Vapour pressure of non-polar fluids and their repulsive and attractive contributions

Using a simple equation of state, based on the Weeks-Chandler-Andersen separation of the intermolecular potential, we have obtained the contributions of repulsive and attractive intermolecular forces to the thermodynamic properties of coexisting vapour and liquid phases of a Lennard-Jones (LJ) fluid.

In order to obtain the vapour pressure of real non-polar fluids, we take the LJ fluid as a reference model, and propose a new perturbative contribution, which is dependant on the temperature and on the acentric factor of the substance. Using the complete perturbed equation, we determine the corresponding repulsive and attractive contributions to the vapour pressure of non-polar fluids. The results show that the attractive vapour pressure of non-polar fluids increases with increasing acentric factor, i.e., larger deviation of the molecular shape from spherical symmetry.

This procedure could be extended to separate the repulsive and attractive contributions of the intermolecular forces to other thermodynamic properties of non-polar fluids as well as of polar fluids and fluid mixtures.     

局域热力学平衡态空气电弧等离子体输运参数计算研究

空气电弧等离子体的物性参数为空气电弧放电过程的仿真提供了可靠的微观理论基础和参数输入. 假定体系处于局域热力学平衡态, 基于Chapman-Enskog理论, 采用Sonine多项式三级展开(对黏滞系数采用二级展开) 得到的输运参数表达式, 数值计算得到了不同气压条件下(0.1 atm-20 atm, 1 atm = 1.01325×10⁵ Pa)、 不同温度范围内(300-30000 K) 空气电弧等离子体的输运参数(扩散系数、黏滞系数、热导率、电导率). 与以往的理论研究相比, 最新的相互作用势和碰撞截面研究成果被应用到涉及粒子的碰撞积分计算中, 提高了输运参数计算结果的精度和可靠性.     

High pressure insulator-metal transition in molecular fluid oxygen

We report the first experimental evidence for a metallic phase in fluid molecular oxygen. Our electrical conductivity measurements of fluid oxygen under dynamic quasi-isentropic compression show that a nonmetal-metal transition occurs at 3.4 fold compression, 4500 K, and 1.2 Mbar. We discuss the main features of the electrical conductivity dependence on density and temperature and give an interpretation of the nature of the electrical transport mechanisms in fluid oxygen at these extreme conditions.     

Mass and thermal transport in liquid Cu-Ag alloys

In this paper, the diffusion, thermodynamic and thermotransport properties in Cu–Ag liquid alloys are extensively investigated with molecular dynamics over a wide composition and temperature range. The simulations are performed with the most reliable EAM potential. The Green-Kubo formalism is employed for calculating transport properties. It is found that the reduced heat of transport in Cu–Ag is very small (about 0.10?eV in absolute value) and almost temperature independent. Further it is found that the interdiffusion coefficient together with both self-diffusion coefficients are almost composition independent. In Cu–Ag, the thermodynamic factor is found to be less than unity whereas the Manning factor is greater than unity (with significant composition and temperature dependence) and their product is very close to 1.     

Microcanonical equilibrium properties of chiral liquid crystals—a Monte Carlo study

Chiral liquid crystals have been investigated by means of a multicanonical Monte Carlo approach in order to characterize their phase behaviour by microcanonical equilibrium properties. The liquid crystals were described by three-dimensional lattice systems with intermolecular interactions given by the chiral Lebwohl-Lasher potential. Self-determined boundary conditions have been applied in order to enable the formation of chiral phases with equilibrium pitch. Selected thermodynamic properties, e.g. microcanonical entropy, temperature, heat capacity and a set of order parameters have been determined with dependence on microcanonical total energy. A cholesteric phase with temperature-induced helix inversion could be proven where the helical superstructure of the single component system studied changed its handedness through an infinite-pitch system. The thermodynamical behaviour in the microcanonical ensemble was found to be very similar to the behaviour in the canonical ensemble. The study of microcanonical equilibrium properties by means of multicanonical Monte Carlo simulations was shown to be a powerful tool for the study of the phase behaviour of model liquid crystals.     

A general isomorphism approach to thermodynamic and transport properties of binary fluid mixtures near critical points

A general isomorphism approach to critical phenomena in binary fluid mixtures that may exhibit complex critical-line behavior is developed by relating the two relevant scaling fields to linear combinations of three physical field variables. These physical field variables are related to the temperature and chemical potentials of the two components. The proposed approach includes crossover from vapor-liquid critical behavior to liquid-liquid critical behavior and incorporates also the critical behavior near other special points on critical loci. It is shown that the key factor which determines the apparent behavior of the thermodynamic and transport properties of near-critical mixtures is the shape of the critical locus. The number of system-dependent coefficients that determine the asymptotic critical behavior is elucidated. The choice of zero-points of entropy and energy in binary mixtures is also discussed. The approach provides a powerful tool for predicting thermodynamic and transport properties of fluid mixtures in the critical region.     

Fractional exclusion statistics applied to relativistic nuclear matter

The effect of statistics of the quasiparticles in the nuclear matter at extreme conditions of density and temperature is evaluated in the relativistic mean-field model generalized to the framework of the fractional exclusion statistics (FES). In the model, the nucleons are described as quasiparticles obeying FES and the model parameters were chosen to reproduce the ground state properties of the isospin-symmetric nuclear matter. In this case, the statistics of the quasiparticles is related to the strengths of the nucleon-nucleon interaction mediated by the neutral scalar and vector meson fields. The relevant thermodynamic quantities were calculated as functions of the nucleons density, temperature and fractional exclusion statistics parameter α. It has been shown that at high temperatures and densities the thermodynamics of the system has a strong dependence on the statistics of the particles. The scenario in which the nucleon-nucleon interaction strength is independent of the statistics of particles was also calculated, but it leads in general to unstable thermodynamics.     

Thermodynamic and transport properties of simple fluids using lattice sums: bulk phases and liquid-vapour interface

Molecular dynamics simulations in the canonical ensemble have been performed to obtain the thermodynamic and transport properties of the Lennard-Jones fluid. The dispersion interactions were calculated using lattice sums. This method makes it possible to simulate the full potential avoiding the inclusion of the long range corrections (LRC) during or at the end of simulations. In the calculation of dynamic properties in bulk phases and thermodynamic quantities of inhomogeneous systems where the interface is physically present, in general the LRC cannot easily be included. By using the lattice sums method, the results are independent of the truncation of the potential. In the liquid-vapour interface simulations it is not necessary to make any pre-judgments about the form of the LRC formula to calculate coexisting properties such as the surface tension. The lattice sums method has been applied to evaluate how well the full interaction can be calculated in the liquid phase and in the liquid-vapour interface. In the liquid phase the pressure, configurational energy, diffusion coefficient and shear viscosity were obtained. The results of the thermodynamic properties are compared with those obtained using the spherically truncated and shifted (STS) potential with the LRC added at the end of simulations, and excellent agreement is found. The transport properties are calculated on different system sizes for a state near the triple point. The diffusion coefficient using the lattice sums method increases with the number of molecules, and the results are higher than those of the STS model truncated at 2.5σ (STS2.5). The shear viscosity does not show any system size dependence for systems with more than 256 molecules, and the lattice sums results are essentially the same as those for the STS2.5. In the liquid-vapour equilibria the coexisting densities and vapour pressures for the full potential agree well with those obtained using the Gibbs ensemble and the NPT + test particle methods. The surface tension using lattice sums and truncation of forces at 2.5σ agrees well with STS results using large system sizes and cutoff distances.     

磁场中非广延相对论费米系统的统计性质

基于广义外势中的非广延统计理论,运用理论解析与数值模拟方法,研究磁场中非广延极端相对论费米气体的热力学性质,给出总能、热容量、化学势的解析式,分析非广延参数、极端相对论效应、磁场及温度对系统热力学性质的影响机理.研究显示,非广延参数不仅对热力学性质有直接的影响,而且也影响着磁场的物理效应. 随温度的升高,非广延参数及磁场对热力学性质的影响均被放大.极端相对论效应对化学势及热容量有特别显著的影响.     

利用重力增压的新型有机工质热力发电循环

与水蒸气朗肯循环给水泵相比,有机朗肯循环工质泵存在技术难度大、效率低、易气蚀和单位功率成本高等问题。本文提出了一种利用重力增压的新型有机工质热力发电循环,冷凝器出口工质不经过泵而依靠重力增压,然后进入蒸发器气化。分别采用R113、R123和R245fa三种干工质分析了不同蒸发温度和冷凝温度下循环所需的重力增压高度。并基于泵的实验数据,比较了该热力循环与泵增压有机朗肯循环的性能。结果表明,相同工作温度下沸点和密度越高的工质所需的重力增压高度越小。在蒸发温度100℃和冷凝温度50℃时,若采用R113,新型循环所需的重力增压高度为22.2 m,热效率为8.1%,比泵增压循环效率高约0 8%。该重力增压循环显示了应用于热电联供领域的潜力。     

Neutron diffraction experiments on a fluid,equimolar mixture of methane and carbon tetrafluoride

A neutron scattering investigation is reported on an equimolar mixture of methane and carbon tetrafluoride along the 370 K isotherm for four different thermodynamic states in a pressure range 270–800 bar, the aim of which was to provide more structural data about this non-ideal system. The fully corrected coherent differential cross-section is presented. The weighted sum of the total atom pair correlation functions is separated into the intramolecular and intermolecular contributions and the structural parameters of the molecules in the fluid state are determined. The density dependence of the intermolecular atom pair correlation functions is clearly visible. The experimental results are compared with previous experiments on the pure components and XRISM calculations, based on a one-centre Lennard-Jones potential.     

Thermodynamic properties of gold–water nanolayer mixtures using molecular dynamics

The physical behavior of a fluid in contact with solid layers is still not fully understood. The present work focuses on the study and understanding of thermodynamic and structural properties of gold–water nanolayer mixtures using molecular dynamics simulations. Two different systems are considered, where approximately 1,700 water molecules are confined between gold nanolayers with separations of 7.4 and 6.2 nm, respectively. Novelties of the present work are in the use of accurate force fields for modeling the inter- and intra-molecular interactions of the components, and providing comprehensive thermodynamic properties of the mixtures. The results are validated by examination of the pure fluid and pure solid properties. Results indicate that the thermodynamics of the system does not behave as an ideal mixture. The structure of the pure fluid is also analyzed and compared against the structure of the confined fluid in the mixture. Anisotropicity is observed in the fluid structure close to the surface of the nanolayer. Higher ordering and higher flux are detected in the fluid molecules close to the fluid–solid interface. Unusual thermodynamic behavior, anisotropicity, liquid layering, and higher interfacial fluid flux could be just some of the factors leading to the enhanced energy transport observed in mixtures involving at least one nanoscale component, such as nanofluids.     

Quantum kinetic theory of polyatomic gases

A review is given of the kinetic theory of polyatomic gases as based on the quantum mechanical Waldmann-Snider kinetic equation. The transport properties in the Navier-Stokes and Burnett regimes and their dependence on external electric and magnetic fields (Senftleben and Senftleben-Beenakker effects) as well as flow and heat-flow birefringence are discussed for gases consisting of linear, spherical top and symmetric top molecules. The relaxation phenomena associated with sound propagation, Rayleigh-Brillouin, depolarized Rayleigh and Raman light scattering are considered in some detail as well as nuclear magnetic and electron spin relaxation and pressure broadening of microwave spectral lines. Finally an overview is given of the quantum mechanical methods for the quantitative calculation of all these phenomena from the nonspherical intermolecular potential.     

Effects of a finite number of particles on the thermodynamic properties of a harmonically trapped ideal charged Bose gas in a constant magnetic field

We investigate the thermodynamic properties of an ideal charged Bose gas confined in an anisotropic harmonic potential and a constant magnetic field. Using an accurate density of states, we calculate analytically the thermodynamic potential and consequently various intriguing thermodynamic properties, including the Bose–Einstein transition temperature, the specific heat, magnetization, and the corrections to these quantities due to the finite number of particles are also given explicitly. In contrast to the infinite number of particles scenarios, we show that those thermodynamic properties,particularly the Bose–Einstein transition temperature depends upon the strength of the magnetic field due to the finiteness of the particle numbers, and the collective effects of a finite number of particles become larger when the particle number decreases. Moreover, the magnetization varies with the temperature due to the finiteness of the particle number while it keeps invariant in the thermodynamic limit N →∞.     

Uncertainty quantification in the catalytic partial oxidation of methane

This work focuses on uncertainty quantification of eight random parameters required as input for 1D modelling of methane catalytic partial oxidation within a highly dense foam reactor. Parameters related to geometrical properties, reactor thermophysics and catalyst loading are taken as uncertain. A widely applied 1D heterogeneous mathematical model that accounts for proper transport and surface chemistry steps is considered for the evaluation of deterministic samples. The non-intrusive spectral projection approach based on polynomial chaos expansion is applied to determine the stochastic temperature and species profiles along the reactor axial direction as well as their ensemble mean and error bars with a confidence interval of 95%. Probability density functions of relevant variables in specific reactor sections are also analysed. A different contribution is noticed from each random input to the total uncertainty range. Porosity, specific surface area and catalyst loading appear as the major sources of uncertainty to bulk gas and surface temperature and species molar profiles. Porosity and the mean pore diameter have an important impact on the pressure drop along the whole reactor as expected. It is also concluded that any trace of uncertainty in the eight input random variables can be almost dissipated near the catalyst outlet section for a long-enough catalyst, mainly due to the approximation to thermodynamic equilibrium.     

Scaling laws for plasma armatures in railguns

A methodology for deriving the electrical and thermodynamic properties of plasma armatures in railgun launchers is presented. The methodology is based on the solution to the one-dimensional, quasi-steady equations for the plasma armature. It is shown that the thermodynamic and transport properties for typical armature materials can be adequately represented by power-law curve fits in the temperature and pressure regimes of interest. To illustrate the methodology, detailed computations for both copper and aluminum armatures are performed. Some discussion is also presented for hydrogen armatures. It is shown that the armature properties predicted by the scaling laws agree very well with those derived from more detailed numerical solutions to the governing differential equations. It is shown that, for both aluminum and copper armatures, the electrical conductivity is a strong function of the current per unit rail height and a weak function of launcher geometry. This dependence is shown to be in reasonable agreement with experimental data compiled over a wide range of gun bore dimensions and operating conditions     

Thermophysical properties of iridium at finite temperature

The bulk properties of materials in an extreme environment such as high temperature and high pressure can be understood by studying anharmonic effects due to the vibration of lattice ions and thermally excited electrons.In this spirit,in the present paper,anharmonic effects are studied by using the recently proposed mean-field potential(MFP) approach and Mermin functional which arise due to the vibration of lattice ions and thermally excited electrons,respectively.The MFP experienced by a wanderer atom in the presence of surrounding atoms is constructed in terms of cold energy using the local form of the pseudopotential.We have calculated the temperature variation of several thermophysical properties in an extreme environment up to melting temperature.The results of our calculations are in excellent agreement with the experimental findings as well as the theoretical results obtained by using first principle methods.We conclude that presently used conjunction scheme(MFP+pseudo potential) is simple computationally,transparent physically,and accurate in the sense that the results generated are comparable and sometimes better than the results obtained by first principle methods.Local pseudopotential used is transferable to extreme environment without adjusting its parameters.     

Transport properties of bulk water at 243–550 K: a Comparative molecular dynamics simulation study using SPC/E,TIP4P,and TIP4P/2005 water models

ABSTRACT

Molecular dynamics simulations of various water models – SPC/E (extended simple point charge), TIP4P (transferable intermolecular potential 4 points), and TIP4P/2005 – have been carried out in the canonical (NVT fixed) ensemble over the range of temperatures 243–550?K with Ewald summation. The transport properties (self-diffusion coefficients D, viscosities η, and thermal conductivities λ) of SPC/E, TIP4P, and TIP4P/2005 water were evaluated at 243–550?K and compared with experimental data. The temperature dependence of transport properties of SPC/E, TIP4P and TIP4P/2005 water was discussed to determine how reliable the models are over this temperature range.     

Energy scales and the non-Fermi liquid behavior in YbRh<Subscript>2</Subscript>Si<Subscript>2</Subscript>

Multiple energy scales are detected in measurements of the thermodynamic and transport properties in heavy fermion metals. We demonstrate that the experimental data on the energy scales can be well described by the scaling behavior of the effective mass at the fermion condensation quantum phase transition, and show that the dependence of the effective mass on temperature and applied magnetic fields gives rise to the non-Fermi liquid behavior. Our analysis is placed in the context of recent salient experimental results. Our calculations of the non-Fermi liquid behavior, of the scales and thermodynamic and transport properties are in good agreement with the heat capacity, magnetization, longitudinal magnetoresistance and magnetic entropy obtained in remarkable measurements on the heavy fermion metal YbRh₂Si₂.